Personal care compositions and methods

ABSTRACT

Methods of making personal care compositions including microcapsules and methods of enhancing the efficacy of the microcapsules in said personal care compositions.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. patent application Ser. No.16/189,360, filed Nov. 13, 2018; which is a continuation of U.S. patentapplication Ser. No. 15/640,675, filed Jul. 3, 2017; which is acontinuation of U.S. patent application Ser. No. 15/412,341, filed onJan. 23, 2017, now U.S. Pat. No. 9,750,671, granted Sep. 5, 2017; whichis a divisional of U.S. patent application Ser. No. 14/755,507, filed onJun. 30, 2015, now U.S. Pat. No. 9,687,425, granted on Jun. 27, 2017,the entire disclosures of which are fully incorporated by reference.

FIELD OF THE INVENTION

The present disclosure generally relates to methods of manufacturingpersonal care compositions that include microcapsules.

BACKGROUND OF THE INVENTION

Personal care compositions have become a staple in the personal hygieneroutine for many people. Personal care compositions can provide benefitsto consumers such as by combating wetness, reducing malodor, and/ordelighting the consumer with the scent of a fragrance. There is,however, room for improvement with respect to the longevity of thefragrance in personal care compositions.

SUMMARY OF THE INVENTION

A method of manufacturing an anhydrous personal care composition, themethod comprising: combining a first process stream at a firsttemperature and a second process stream at a second temperature, whereinthe first process stream comprises a material selected from the groupconsisting of a structurant, a solvent, and combinations thereof, andthe second process stream comprises a plurality of microcapsules;wherein the second temperature does not exceed 80° C.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram of a split stream manufacturing process.

DETAILED DESCRIPTION OF THE INVENTION I. Definitions

As used herein, the following terms shall have the meaning specifiedthereafter:

“Ambient” refers to surrounding conditions at about one atmosphere ofpressure, about 50% relative humidity, and about 25° C.

“Anhydrous” refers to compositions and/or components which aresubstantially free of water or free of water.

“Free of” means that the stated ingredient has not been added to thepersonal care composition. However, the stated ingredient mayincidentally form as a byproduct or a reaction product of the othercomponents of the personal care composition.

“Personal care composition” refers to compositions, including but notlimited to, creams, gels, solid sticks, aerosols, and soft-solid sticks.For example, the personal care composition may be a composition such asa soft-solid deodorant, soft-solid antiperspirant, an invisible soliddeodorant, an invisible solid antiperspirant, aerosol antiperspirant,fluid antiperspirant, body powder, or foot powder.

“Onset of crystallization” means the temperature at which a materialcrystallizes from a liquid solution. All melting points and onsets ofcrystallization referenced herein, unless otherwise specified, aremeasured by the well known technique of Differential Scanningcalorimetry (DSC). For evaluation, a Perkin-Elmer 7 Series ThermalAnalysis System Model DSC7 manufactured by Perkin-Elmer, Norwalk, Conn.is used.

“PMC” refers to microcapsules having a shell encapsulating a corematerial, where the core material includes at least one benefit agent.

“Soft solid” refers to a composition with a static yield stress of about200 Pa to about 1,500 Pa after dispensing.

“Substantially free of” refers to about 2% or less, about 1% or less, orabout 0.1% or less of a stated ingredient by weight of the personal carecomposition.

II. High Temperatures and Fragrance Release from Microcapsules

Initial tries to manufacture anhydrous personal care compositions thatincorporated PMCs resulted in failures when the personal carecompositions were made via a batch process. It was initially believedthat there was an ingredient included within the personal carecomposition that was interfering with the PMCs. Several attempts weremade to identify the incompatible ingredient, but such an ingredient wasnever identified.

It has been surprisingly discovered that the prolonged exposure ofpersonal care compositions containing microcapsules to high levels ofheat may result in a significant reduction in the release of thefragrance from the microcapsules. For reasons unknown, the exposure tohigh levels of heat (i.e. >40° C.) when manufacturing the personal carecomposition has been found to impact the amount of fragrance releasedinto the headspace by the microcapsules.

The impact of high levels of heat was unexpected as for at least some ofthe microcapsules, for example the polyacrylate microcapsules used inthe Examples herein, because the glass transition temperature of themicrocapsules in many cases far exceeded that temperatures used inmanufacturing the personal care compositions. In this regard, formicrocapsules encapsulating a liquid, such as a liquid fragrance, theglass transition temperature of the microcapsules and the glasstransition temperature of the shell of said microcapsule are typicallyabout the same. For at least some of the microcapsules provided hereinsuch as for the polyacrylate microcapsules, the microcapsules may have ashell with a glass transition temperature that is less than or equal to75-150 degrees Celsius. Thus, although the glass transition temperatureof the microcapsules exceeded the processing temperature for themanufacture of the personal care composition, exposure of themicrocapsules to the high levels of heat still impacted the performanceof the microcapsules. Without being bound by theory, it is believed thatthe high levels of heat during the manufacturing of the personal carecomposition may result in the extraction of the fragrance from themicrocapsule over time.

The reduction in fragrance release upon exposure to high levels of heatwas observed with microcapsules whose shell materials containedsynthetic polymers and with microcapsules whose shell materialscontained naturally-occurring polymers. Because prolonged exposure ofpersonal care compositions to high temperatures is common during theproduction of many types of personal care compositions, includingantiperspirant compositions, creating a process that substantiallyminimizes the amount of heat and the time of exposure to said heat islikely to improve the performance (i.e. fragrance release) ofmicrocapsules in personal care compositions.

In this regard, Table 2 illustrates the effect of a prolonged exposureof personal care compositions containing PMCs to high temperatures whenprepared using a batch process. Example A is a soft solid antiperspirantcomposition containing fragrance-loaded polyacrylate microcapsules, madeusing a batch process. Example B is an invisible solid, antiperspirantcomposition containing fragrance-loaded polyacrylate microcapsules, madeusing a batch process. Example D is a personal care compositioncontaining fragrance-loaded polyacrylate microcapsules andcyclopentasiloxane, made by a batch process. Example E is a personalcare composition containing fragrance-loaded polyacrylate microcapsulesand dimethicone, made by a batch process. Example F is a personal carecomposition containing fragrance-loaded gelatin microcapsules anddimethicone, made by a batch process.

The results illustrated below in Table 2 were generated using theheadspace test method described herein, with the following settings:manufacturer standard settings were used with a 10 second pump forExamples A, B, D, E and F. The analysis of Examples A and B wasconducted using a 40° C. sensor temperature. The analysis of Examples D,E and F was conducted using a 60° C. sensor temperature. Each examplewas held at an elevated temperature for 72 hours. Examples A, B, and Dwere each held at 73° C. for 72 hours while Examples E and F were heldat 75° C. for 72 hours. The percent decrease is calculated according tothe following equation: ((Initial Headspace Value−72 Hour Headspacevalue)/Initial Headspace Value)*100%.

For Example A, exposure to 73° C. for 48 hours decreased the amount offragrance released into the headspace from an initial headspace count of12929 to a count of 6421. Exposure of Example A to 73° C. for 72 hoursfurther decreased the amount of fragrance released into the headspace toa count of 4123. For Example B, exposure to 73° C. for 72 hoursdecreased the amount of fragrance released into the headspace from aninitial headspace count of 8754 to a count of 1637. For Example D,exposure to 73° C. for 72 hours decreased the amount of fragrancereleased into the headspace from an initial headspace count of 55764 toa count of 21856. For Example E, exposure to 73° C. for 48 hoursdecreased the amount of fragrance released into the headspace from aninitial headspace count of 30088 to a count of 13818. Exposure ofExample E to 75° C. for 72 hours further decreased the amount offragrance released into the headspace to a count of 11524. For ExampleF, exposure to 73° C. for 48 hours decreased the amount of fragrancereleased into the headspace from an initial headspace count of 22057 toa count of 9536. Exposure of Example F to 75° C. for 72 hours decreasedthe amount of fragrance released into the headspace from an initialheadspace count of 22057 to a count of 11856. Additionally, exposure ofa soft solid or invisible solid to 73° C. for 24 hours also resulted indecreases in the performance of microcapsules (data not shown). Thesedata suggest that the prolonged exposure of a personal compositioncontaining fragrance-loaded microcapsules to high temperatures (e.g. atleast 72° C.) results in a reduction in the release of fragrance fromthe microcapsules. The data further suggests that microcapsules whoseshell materials are made using synthetic polymers and microcapsuleswhose shell materials are made using naturally-occurring polymers arelikely both susceptible to prolonged exposures to elevated temperaturesduring the manufacturing of the personal care composition.

TABLE 2 peak area analyzed 48 hr 72 hr Percent Example Composition PMCType Initial exposure exposure Decrease A Soft Solid Polyacrylate 129296421 4123 68.1% B Invisible Solid Polyacrylate 8754 — 1637 81.3% DCyclopentasiloxane Polyacrylate 55764 — 21856 60.8% E DimethiconePolyacrylate 30088 13818 11524 61.7% F Dimethicone Gelatin 22057 953611856 46.2%

Table 3, below, illustrates the affect of a prolonged exposure ofpersonal care compositions containing fragrance-loaded microcapsules toa range of temperatures ranging from 40° C. to 80° C. during a batchprocess. The results illustrated in Table 3 were generated using theheadspace test method described herein, with the following settings:manufacturer standard settings were used with a 10 second pump and 60°C. sensor for Examples E and F. All Examples were held at thetemperature indicated in Table 3 for 72 hours. The Percent decrease iscalculated according to the following equation: ((Initial HeadspaceValue−72 Hour Headspace value)/Initial Headspace Value)*100%.

Referring to Table 3, Examples E and F were subjected to temperaturesranging from 40° C. to 80° C. The initial headspace values for ExamplesE and F were derived from samples prior to being subjected to elevatedtemperatures. As can be seen from Table 3, prolonged exposure to atemperature of at least 50° C. for 72 hours was sufficient to cause adecrease in the performance of Example E as demonstrated by the 21.6%decrease in the headspace counts. Prolonged exposure to a temperature ofat least 55° C. for 72 hours was sufficient to cause a decrease in theperformance of Example E and Example F as demonstrated by the 38.9% and48.7% decrease, respectively, in the headspace counts. Prolongedexposure of Examples E and F to a temperature greater than 60° C.further decreased the performance of the microcapsules in said examples.These data suggest that the prolonged exposure of personal compositioncontaining fragrance-loaded microcapsules to high temperatures (e.g.greater than 40° C.) results in a reduction in the release of fragrancefrom the microcapsules and that said reduction occurs for bothmicrocapsules whose shell materials are made using synthetic polymersand for microcapsules whose shell materials are made usingnaturally-occurring polymers.

TABLE 3 % Decrease vs. initial headpspace value Example E Example FTemperature (Percent Decrease) (Percent Decrease) (° C.) PolyacrylatePMC Gelatin PMC 40 −3.4% — 50 21.6% — 55 38.9% 48.7% 60 28.6% — 70 56.7%— 75 62.0% 46.2% 80 46.6% —

Although it is not uncommon for personal care compositions to besubjected to temperatures greater than 40° C. for prolonged periods oftime during the manufacturing process, the data illustrated in Tables 2and 3 demonstrate that such temperatures may negatively impact theperformance of fragrance-loaded microcapsules in such personal carecompositions. The data shown in Table 4, generated using the headspacetest method described herein, demonstrates at least two different waysof manufacturing a personal care composition containing fragrance-loadedmicrocapsules without significantly impairing the performance of themicrocapsules.

TABLE 4 Example Initial Held for 72 Hours at 73° C. B 8754 1637 C 7185 —

Referring to Table 4, Example B represents an invisible solid made by abatch process and Example C is an invisible solid, antiperspirantcomposition containing fragrance-loaded polyacrylate microcapsules madeby a split stream process where the fragrance-loaded microcapsules wereadded via the second process stream, as described herein. Example B wassubjected to 73° C. for one hour for 72 hours. Example B had an initialheadspace count of 8754 after a one hour exposure to 73° C. Exposure ofExample B to 73° C. for 72 hours decreased the head space count to 1637.In contrast, Example C had an initial head space count of 7185. Thesedata suggest that while the batch process may be used to manufacturepersonal care compositions containing fragrance-loaded microcapsules,exposure to high levels of heat for extended periods of time during theprocess may impact the performance of the microcapsules in the personalcare compositions. Further, it is likely that placing thefragrance-loaded microcapsules into the first process stream of thesplit stream process may also impact the performance of themicrocapsules due to the prolonged exposure to high levels of heat.

To minimize the exposure of the microcapsules to high levels of heatduring the manufacture of personal care compositions, the following aresuggested improvements to existing methods:

-   -   1) Use of a split stream process, as described herein, where the        PMCs are included within the second process stream.    -   2) Applying the concept of Late Point Product Differentiation        described herein such as by adding the microcapsules to the        personal care composition when the temperature of the personal        care composition is less than 80° C., less than 70° C., less        than 60° C., less than 55° C., or less than 50° C., but above        the temperature at which point the personal care composition        solidifies.    -   3) A batch process to produce personal care compositions        containing PMCs may require monitoring the temperature of the        holding tank containing the personal care composition to ensure        the personal care composition is not subjected to temperatures        that are shown above to impact the performance of the        microcapsules. In some cases, the temperatures of the personal        care composition should not be subject to temperatures greater        than 60° C. for more than 72 hours when the microcapsules are        polyacrylate microcapsule, and not subject to temperatures        greater than 55° C. for more than 72 hours when the        microcapsules' shell include gelatin. In some instances, it may        not be desirable to exceed 55° C. for more than 24 hours.

Antiperspirant Active

Antiperspirant compositions may include an antiperspirant activesuitable for application to human skin. The concentration of theantiperspirant active in the antiperspirant composition should besufficient to provide the desired enhanced wetness protection. Forexample, the active may be present in an amount of from about 0.1%,about 0.5%, about 1%, or about 5%; to about 60%, about 35%, about 25% orabout 20%, by weight of the antiperspirant composition. These weightpercentages are calculated on an anhydrous metal salt basis exclusive ofwater and any complexing agents such as glycine, glycine salts, or othercomplexing agents.

An antiperspirant active may include any compound, composition, or othermaterial having antiperspirant activity. Such actives may includeastringent metallic salts, like inorganic and organic salts of aluminum,zirconium and zinc, as well as mixtures thereof. For example, theantiperspirant active may include zirconium-containing salts ormaterials, such as zirconyl oxyhalides, zirconyl hydroxyhalides, andmixtures thereof; and/or aluminum-containing salts such as, for example,aluminum halides, aluminum chlorohydrate, aluminum hydroxyhalides, andmixtures thereof.

1. Aluminum Salts

Aluminum salts useful herein may include those that conform to theformula:

Al₂(OH)_(a)Cl_(b) .xH₂O

wherein a is from about 2 to about 5; the sum of a and b is about 6; xis from about 1 to about 6; where a, b, and x may have non-integervalues. For example, aluminum chlorohydroxides referred to as “⅚ basicchlorohydroxide,” wherein a is about 5 and “⅔ basic chlorohydroxide”,wherein a=4 may be used.

A general description of these aluminum salts may be found inAntiperspirants and Deodorants, Cosmetic Science and Technology SeriesVol. 20, 2^(nd) edition, edited by Karl Laden. Mixtures of aluminumsalts are described in British Patent Specification 1,347,950, filed inthe name of Shin et al. and published Feb. 24, 1974.

2. Zirconium Salts

Zirconium salts useful herein may include those which conform to theformula:

ZrO(OH)_(2-a)Cl_(a) .xH₂O

wherein a is from about 1.5 to about 1.87; x is from about 1 to about 7;and wherein a and x may both have non-integer values. These zirconiumsalts are described in Belgian Patent 825,146, issued to Schmitz on Aug.4, 1975. Useful to the present invention are zirconium salt complexesthat additionally contain aluminum and glycine, commonly known as “ZAGcomplexes”. These complexes may contain aluminum chlorohydroxide andzirconyl hydroxy chloride conforming to the above-described formulas.Examples of two such complexes include aluminum zirconiumtrichlorohydrex and aluminum zirconium tetrachlorohydrex.

Structurants

Personal care compositions may also include a structurant to helpprovide the personal care composition with the desired viscosity,rheology, texture and/or product hardness, or to otherwise help suspendany dispersed solids or liquids within the personal care composition.The term “structurant” may include any material known or otherwiseeffective in providing suspending, gelling, viscosifying, solidifying,or thickening properties to the personal care composition or whichotherwise provide structure to the final product form. Non-limitingexamples of structurants include, for example, gelling agents, polymericor nonpolymeric agents, inorganic thickening agents, or viscosifyingagents. Non-limiting examples of thickening agents include, for example,organic solids, silicone solids, crystalline or other gellants,inorganic particulates such as clays or silicas, or combinationsthereof.

The concentration and type of the structurant selected for use in thepersonal care composition may vary depending upon the desired productform, viscosity, and hardness. The thickening agents suitable for useherein, may have a concentration range from about 0.1%, about 3%, orabout 5%; to about 35%, about 20%, or about 10%, by weight of thepersonal care composition. Soft solids will often contain a lower amountof structurant than solid compositions. For example, a soft solid maycontain from about 1.0% to about 9%, by weight of the composition, whilea solid composition may contain from about 15% to about 25%, by weightof the personal care composition, of a structurant. This is not a hardand fast rule, however, as a soft solid product with a higherstructurant value may be formed by, for example, shearing the product asit is dispensed from a package.

Non-limiting examples of suitable gelling agents include fatty acidgellants, salts of fatty acids, hydroxyl acids, hydroxyl acid gellants,esters and amides of fatty acid or hydroxyl fatty acid gellants,cholesterolic materials, dibenzylidene alditols, lanolinolic materials,fatty alcohols, triglycerides, sucrose esters such as SEFA behenate,inorganic materials such as clays or silicas, other amide or polyamidegellants, and mixtures thereof. Optionally, the microcapsules may bepremixed with such gellants prior to incorporation into the personalcare composition.

Suitable gelling agents include fatty acid gellants such as fatty acidand hydroxyl or alpha hydroxyl fatty acids, having from about 10 toabout 40 carbon atoms, and ester and amides of such gelling agents.Non-limiting examples of such gelling agents include, but are notlimited to, 12-hydroxystearic acid, 12-hydroxylauric acid,16-hydroxyhexadecanoic acid, behenic acid, eurcic acid, stearic acid,caprylic acid, lauric acid, isostearic acid, and combinations thereof.Preferred gelling agents are 12-hydroxystearic acid, esters of12-hydroxystearic acid, amides of 12-hydroxystearic acid andcombinations thereof.

Other suitable gelling agents include amide gellants such asdi-substituted or branched monoamide gellants, monosubstituted orbranched diamide gellants, triamide gellants, and combinations thereof,including n-acyl amino acid derivatives such as n-acyl amino acidamides, n-acyl amino acid esters prepared from glutamic acid, lysine,glutamine, aspartic acid, and combinations thereof. Other suitable amidegelling agents are described in U.S. Pat. No. 5,429,816, issued Jul. 4,1995, and U.S. Pat. No. 5,840,287, filed Dec. 20, 1996.

Still other examples of suitable gelling agents include fatty alcoholshaving at least about 8 carbon atoms, at least about 12 carbon atoms butno more than about 40 carbon atoms, no more than about 30 carbon atoms,or no more than about 18 carbon atoms. For example, fatty alcoholsinclude but are not limited to cetyl alcohol, myristyl alcohol, stearylalcohol and combinations thereof.

Non-limiting examples of suitable triglyceride gellants includetristearin, hydrogenated vegetable oil, trihydroxystearin (Thixcin® R,available from Rheox, Inc.), rape seed oil, castor wax, fish oils,tripalmitin, Syncrowax® HRC and Syncrowax® HGL-C(Syncrowax® availablefrom Croda, Inc.).

Other suitable thickening agents include waxes or wax-like materialshaving a melt point of above 65° C., more typically from about 65° C. toabout 130° C., examples of which include, but are not limited to, waxessuch as beeswax, carnauba, bayberry, candelilla, montan, ozokerite,ceresin, hydrogenated castor oil (castor wax), synthetic waxes andmicrocrystalline waxes. The synthetic wax may be, for example, but notlimited to, a polyethylene, a polymethylene, or a combination thereof.Some suitable polymethylenes may have a melting point from about 65° C.to about 75° C. Examples of some suitable polyethylenes include thosewith a melting point from about 60° C. to about 95° C. Other highmelting point waxes are described in U.S. Pat. No. 4,049,792, Elsnau,issued Sep. 20, 1977.

Further structurants for use in the personal care compositions mayinclude inorganic particulate thickening agents such as clays andcolloidal pyrogenic silica pigments. For example, but not limited to,colloidal pyrogenic silica pigments such as Cab-O-Sil®, a submicroscopicparticulated pyrogenic silica may be used. Other known or otherwiseeffective inorganic particulate thickening agents that are commonly usedin the art may also be used in the personal care compositions describedherein. Concentrations of particulate thickening agents may range, forexample, from about 0.1%, about 1%, or about 5%; to about 35%, about15%, about 10% or about 8%, by weight of the personal care composition.

Clay structurants include montmorillonite clays, non-limiting examplesof which include bentonites, hectorites, and colloidal magnesiumaluminum silicates. These and other clays may be hydrophobicallytreated, and when treated will generally be used in combination with aclay activator. Non-limiting examples of suitable clay activatorsinclude propylene carbonate, ethanol, and combinations thereof. Whenclay activators are present, the amount of clay activator may be in arange of from about 40%, about 25%, or about 15%; to about 75%, about60%, or about 50%, by weight of the clay.

Surfactant

The personal care compositions may include a surfactant. A surfactant isgenerally present at a level of about 0.05% to about 5%, by weight ofthe personal care composition, but may contain, from about 0.5% to about5.0%; from about 1.0% to about 4%; from about 1.5% to about 3.5%; fromabout 1.75% to about 2.5%; about 2%, or any combination thereof. Thesurfactant may have a HLB range of about 2 to about 14; about 6 to about12; about 8 to about 10; or any combination thereof. The surfactant maybe free of polyoxyethylene sorbitan fatty acids. The surfactant maycomprise, for example, a C₂₀₋₄₀ Pareth-10. Another suitable surfactantis a nonionic ethoxylated linear alcohol with a carbon chain length of20-40. Suitable surfactants include PERFORMATHOX™ 450 ethoxylate.

Anhydrous Liquid Carrier

Personal care compositions may also include anhydrous liquid carriers.The anhydrous liquid carrier may be present, for example, atconcentrations ranging from about 10%, about 15%, about 20%, about 25%;to about 99%, about 70%, about 60%, or about 50%, by weight of thepersonal care composition. Such concentrations will vary depending uponvariables such as product form, desired product hardness, and selectionof other ingredients in the personal care composition. The anhydrouscarrier may be any anhydrous carrier known for use in personal carecompositions or otherwise suitable for topical application to the skin.For example, anhydrous carriers may include, but are not limited to,volatile and nonvolatile fluids.

A. Volatile Fluid

The personal care compositions may also include a volatile fluid such asa volatile silicone carrier. Volatile fluids are present, for example,at concentrations ranging from about 20% or from about 30%; to about80%, or no about 60%, by weight of the personal care composition. Thevolatile silicone of the solvent may be cyclic, linear, and/or branchedchain silicone. “Volatile silicone”, as used herein, refers to thosesilicone materials that have measurable vapor pressure under ambientconditions. Non-limiting examples of suitable volatile silicones aredescribed in Todd et al., “Volatile Silicone Fluids for Cosmetics”,Cosmetics and Toiletries, 91:27-32 (1976).

The volatile silicone may be a cyclic silicone. The cyclic silicone mayhave from about 3 silicone atoms, or from about 5 silicone atoms; toabout 7 silicone atoms, or to about 6 silicone atoms. For example,volatile silicones may be used which conform to the formula:

wherein n is from about 3, or from about 5; to about 7, or to about 6.These volatile cyclic silicones generally have a viscosity of less thanabout 10 centistokes at 25° C. Suitable volatile silicones for useherein include, but are not limited to, Cyclomethicone D5 (commerciallyavailable from G. E. Silicones); Dow Corning 344, and Dow Corning 345(commercially available from Dow Corning Corp.); and GE 7207, GE 7158and Silicone Fluids SF-1202 and SF-1173 (available from General ElectricCo.). SWS-03314, SWS-03400, F-222, F-223, F-250, F-251 (available fromSWS Silicones Corp.); Volatile Silicones 7158, 7207, 7349 (availablefrom Union Carbide); Masil SF-V (available from Mazer) and combinationsthereof.

B. Non-Volatile Fluid

A non-volatile fluid may also be present, for example, at concentrationsranging from about 1%, from about 2%; to about 20%, or about 15%, byweight of the personal care composition.

1. Non-Volatile Organic Fluids

The non-volatile organic fluid may be present at concentrations rangingfrom about 1%, from about 2% but no more than about 20% or no more thanabout 15%, by weight of the personal care composition.

Non-limiting examples of nonvolatile organic fluids include, but are notlimited to, mineral oil, PPG-14 butyl ether, isopropyl myristate,petrolatum, butyl stearate, cetyl octanoate, butyl myristate, myristylmyristate, C12-15 alkylbenzoate (e.g., Finsolv™), dipropylene glycoldibenzoate, PPG-15 stearyl ether benzoate and blends thereof (e.g.Finsolv TPP), neopentyl glycol diheptanoate (e.g. Lexfeel 7 supplied byInolex), octyldodecanol, isostearyl isostearate, octododecyl benzoate,isostearyl lactate, isostearyl palmitate, isononyl/isononoate,isoeicosane, octyldodecyl neopentanoate, hydrogenated polyisobutane, andisobutyl stearate. Many such other carrier liquids are disclosed in U.S.Pat. No. 6,013,248 (Luebbe et al.) and U.S. Pat. No. 5,968,489 (Swaileet al.).

2. Nonvolatile Silicone Fluids

The personal care composition may also include a non-volatile siliconefluid. The non-volatile silicone fluid may be a liquid at or below humanskin temperature, or otherwise in liquid form within a personal carecomposition, like an anhydrous antiperspirant composition, during orshortly after topical application. The concentration of the non-volatilesilicone may be from about 1%, from about 2%; to about 15%, about 10%,by weight of the personal care composition. Nonvolatile silicone fluidsmay include those which conform to the formula:

wherein n is greater than or equal to 1. These linear silicone materialsmay generally have viscosity values of from about 5 centistokes, fromabout 10 centistokes; to about 100,000 centistokes, about 500centistokes, about 200 centistokes, or about 50 centistokes, as measuredunder ambient conditions.

Specific non limiting examples of suitable nonvolatile silicone fluidsinclude Dow Corning 200, hexamethyldisiloxane, Dow Corning 225, DowCorning 1732, Dow Corning 5732, Dow Corning 5750 (available from DowCorning Corp.); and SF-96, SF-1066 and SF18(350) Silicone Fluids(available from G.E. Silicones).

Low surface tension non-volatile solvent may be also be used. Suchsolvents may be selected from the group consisting of dimethicones,dimethicone copolyols, phenyl trimethicones, alkyl dimethicones, alkylmethicones, and mixtures thereof. Low surface tension non-volatilesolvents are also described in U.S. Pat. No. 6,835,373 (Kolodzik etal.).

Malodor Reducing Agent

The personal care composition may also include a malodor reducing agent.Malodor reducing agents include components other than the antiperspirantactive within the personal care composition that act to eliminate theeffect that body odor has on fragrance display. These agents may combinewith the offensive body odor so that they are not detectable includingand may suppress the evaporation of malodor from the body, absorb sweator malodor, mask the malodor, and/or prevent/inhibit microbiologicalactivity from odor causing organisms. The concentration of the malodorreducing agent within the personal care composition should be sufficientto provide such chemical or biological means for reducing or eliminatingbody odor. Although the concentration will vary depending on the agentused, generally, the malodor reducing agent may be included within thepersonal care composition from about 0.05%, about 0.5%, or about 1%; toabout 15%, about 10%, or about 6%, by weight of the personal carecomposition.

Malodor reducing agents may include, but are not limited to, pantothenicacid and its derivatives, petrolatum, menthyl acetate, uncomplexedcyclodextrins and derivatives thereof, talc, silica and mixturesthereof. Such agents may be used as described in U.S. Pat. No.6,495,149, issued to Scavone, et al. and U.S. patent application2003/0152539, filed Jan. 25, 2002 in the names of Scavone, et al.

For example, if panthenyl triacetate is used, the concentration of themalodor reducing agent may be from about 0.1% or about 0.25%; to about3.0%, or about 2.0%, by weight of the personal care composition. Anotherexample of a malodor reducing agent is petrolatum which may be includedfrom about 0.10%, or about 0.5%; to about 15%, or about 10%, by weightof the personal care composition. A combination may also be used as themalodor reducing agent including, but not limited to, panthenyltriacetate and petrolatum at levels from about 0.1%, or 0.5%; to about3.0%, or about 10%, by weight of the personal care composition. Menthylacetate, a derivative of menthol that does not have a cooling effect,may be included from about 0.05%, or 0.01%; to about 2.0%, or about1.0%, by weight of the personal care composition. The malodor reducingagent(s) may be in the form of a liquid or a semi-solid such that itdoes not contribute to product residue.

Microcapsules

The personal care compositions herein may include microcapsules. Themicrocapsules may be any kind of microcapsule disclosed herein or knownin the art. The microcapsules may have a shell and a core materialencapsulated by the shell. The core material of the microcapsules mayinclude one or more fragrances. The shells of the microcapsules may bemade from synthetic polymeric materials or naturally-occurring polymers.Synthetic polymers can be derived from petroleum oil, for example.Non-limiting examples of synthetic polymers include nylon,polyethylenes, polyamides, polystyrenes, polyisoprenes, polycarbonates,polyesters, polyureas, polyurethanes, polyolefins, polysaccharides,epoxy resins, vinyl polymers, polyacrylates, and mixtures thereof.Non-limiting examples of suitable shell materials include materialsselected from the group consisting of reaction products of one or moreamines with one or more aldehydes, such as urea cross-linked withformaldehyde or gluteraldehyde, melamine cross-linked with formaldehyde;gelatin-polyphosphate coacervates optionally cross-linked withgluteraldehyde; gelatin-gum Arabic coacervates; cross-linked siliconefluids; polyamine reacted with polyisocyanates; acrylate monomerspolymerized via free radical polymerization, and mixtures thereof.Natural polymers occur in nature and can often be extracted from naturalmaterials. Non-limiting examples of naturally occurring polymers aresilk, wool, gelatin, cellulose, proteins, and combinations thereof.

The microcapsules may be friable microcapsules. A friable microcapsuleis configured to release its core material when its shell is ruptured.The rupture can be caused by forces applied to the shell duringmechanical interactions. The microcapsules may have a median volumeweighted fracture strength of from about 0.1 MPa to about 25.0 MPa, whenmeasured according to the Fracture Strength Test Method, or anyincremental value expressed in 0.1 mega Pascals in this range, or anyrange formed by any of these values for fracture strength. As anexample, the microcapsules may have a median volume weighted fracturestrength of 0.5-25.0 mega Pascals (MPa), alternatively from 0.5-20.0mega Pascals (MPa), 0.5-15.0 mega Pascals (MPa), or alternatively from0.5-10.0 mega Pascals (MPa).

The microcapsules may have a median volume-weighted particle size offrom 2 microns to 80 microns, from 10 microns to 30 microns, or from 10microns to 20 microns, as determined by the Test Method for DeterminingMedian Volume-Weighted Particle Size of Microcapsules described herein.

The microcapsules may have various core material to shell weight ratios.The microcapsules may have a core material to shell ratio that isgreater than or equal to: 10% to 90%, 30% to 70%, 50% to 50%, 60% to40%, 70% to 30%, 75% to 25%, 80% to 20%, 85% to 15%, 90% to 10%, and 95%to 5%.

The microcapsules may have shells made from any material in any size,shape, and configuration known in the art. Some or all of the shells mayinclude a polyacrylate material, such as a polyacrylate randomcopolymer. For example, the polyacrylate random copolymer can have atotal polyacrylate mass, which includes ingredients selected from thegroup including: amine content of 0.2-2.0% of total polyacrylate mass;carboxylic acid of 0.6-6.0% of total polyacrylate mass; and acombination of amine content of 0.1-1.0% and carboxylic acid of 0.3-3.0%of total polyacrylate mass.

When a microcapsule's shell includes a polyacrylate material, thepolyacrylate material may form 5-100% of the overall mass, or anyinteger value for percentage in this range, or any range formed by anyof these values for percentage, of the shell. As examples, thepolyacrylate material may form at least 5%, at least 10%, at least 25%,at least 33%, at least 50%, at least 70%, or at least 90% of the overallmass of the shell.

The microcapsules may have various shell thicknesses. The microcapsulesmay have a shell with an overall thickness of 1-2000 nanometers, or anyinteger value for nanometers in this range, or any range formed by anyof these values for thickness. As a non-limiting example, themicrocapsules may have a shell with an overall thickness of 2-1100nanometers.

The microcapsules may also encapsulate one or more benefit agents. Thebenefit agent(s) include, but are not limited to, one or more ofchromogens, dyes, cooling sensates, warming sensates, fragrances, oils,pigments, in any combination. When the benefit agent includes afragrance, said fragrance may comprise from about 2% to about 80%, fromabout 20% to about 70%, from about 30% to about 60% of a perfume rawmaterial with a C log P greater than −0.5, or even from about 0.5 toabout 4.5. In some examples, the fragrance encapsulated may have a C logP of less than 4.5, less than 4, or less than 3. In some examples, themicrocapsule may be anionic, cationic, zwitterionic, or have a neutralcharge. The benefit agents(s) can be in the form of solids and/orliquids. The benefit agent(s) include any kind of fragrance(s) known inthe art, in any combination.

The microcapsules may encapsulate an oil soluble material in addition tothe benefit agent. Non-limiting examples of the oil soluble materialinclude mono, di- and tri-esters of C₄-C₂₄ fatty acids and glycerine;butyl oleate; hydrogenated castor oil; castor oil; mineral oil;capryllic triglyceride; vegetable oil; geranyl palmitate; silicone oil;isoproplyl myristate, soybean oil, hexadecanoic acid, methyl ester,isododecane, and combinations thereof, in addition to the encapsulatedbenefit agent. The oil soluble material may have a C log P about 4 orgreater, at least 4.5 or greater, at least 5 or greater, at least 7 orgreater, or at least 11 or greater.

The microcapsule's shell may comprise a reaction product of a firstmixture in the presence of a second mixture comprising an emulsifier,the first mixture comprising a reaction product of i) an oil soluble ordispersible amine with ii) a multifunctional acrylate or methacrylatemonomer or oligomer, an oil soluble acid and an initiator, theemulsifier comprising a water soluble or water dispersible acrylic acidalkyl acid copolymer, an alkali or alkali salt, and optionally a waterphase initiator. In some examples, said amine is an aminoalkyl acrylateor aminoalkyl methacrylate.

The microcapsules may include a core material and a shell surroundingthe core material, wherein the shell comprises: a plurality of aminemonomers selected from the group consisting of aminoalkyl acrylates,alkyl aminoalkyl acrylates, dialkyl aminoalykl acrylates, aminoalkylmethacrylates, alkylamino aminoalkyl methacrylates, dialkyl aminoalyklmethacrylates, tertiarybutyl aminethyl methacrylates, diethylaminoethylmethacrylates, dimethylaminoethyl methacrylates, dipropylaminoethylmethacrylates, and mixtures thereof; and a plurality of multifunctionalmonomers or multifunctional oligomers.

Non-limiting examples of microcapsules include microcapsules thatcomprise a shell comprising an amine selected from the group consistingof diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate,tertiarybutyl aminoethyl methacrylate; and combinations thereof; a corematerial encapsulated by said shell, said core material comprising about10% to about 60% of a material selected from the group consisting ofmono, di- and tri-esters of C₄-C₂₄ fatty acids and glycerine; isoproplylmyristate, soybean oil, hexadecanoic acid, methyl ester, isododecane,and combinations thereof, by weight of the microcapsule; and about 10%to about 90% of a perfume material, by weight of the microcapsule;wherein said microcapsules have a volume weighted fracture strength from0.1 MPa to 25 MPa, preferably from 0.8 MPa to 20 MPa, more preferablyfrom 1.0 MPa to 15 MPa; wherein said microcapsules have a medianvolume-weighted particle size from 10 microns to 30 microns.

Processes for making microcapsules are well known. Various processes formicroencapsulation, and exemplary methods and materials, are set forthin U.S. Pat. Nos. 6,592,990; 2,730,456; 2,800,457; 2,800,458; 4,552,811;and U.S. 2006/0263518 A1.

The microcapsule may be spray-dried to form spray-dried microcapsules.

The personal care compositions may also include a parent fragrance andone or more encapsulated fragrances that may or may not differ from theparent fragrance. For example, the composition may include a parentfragrance and a non-parent fragrance. A parent fragrance refers to afragrance that is dispersed throughout the composition and is typicallynot encapsulated when added to the composition. Herein, a non-parentfragrance refers to a fragrance that differs from a parent fragrance andis encapsulated with an encapsulating material prior to inclusion into acomposition. Non-limiting examples of differences between a fragranceand a non-parent fragrance include differences in chemical make-up.

Some fragrances may be considered to be volatile and other fragrancesmay be considered to be or non-volatile, as described and definedherein. The term “non-volatile,” as used herein, unless otherwisespecified, refers to those materials that are liquid under ambientconditions and which have a measurable vapor pressure at 25° C. Thesematerials typically have a vapor pressure less than about 0.01 mmHg, andan average boiling point typically greater than about 250° C. The term“volatile,” as used herein, unless otherwise specified, refers to thosematerials that are liquid under ambient conditions and which have ameasurable vapor pressure at 25° C. These materials typically have avapor pressure greater than about 0.01 mmHg, more typically from about0.02 mmHg to about 20 mmHg, and an average boiling point typically lessthan about 250° C., more typically less than about 235° C.

Other Fragrance Delivery Systems

The composition may also contain one or more other delivery systems forproviding one or more benefit agents, in addition or in place of themicrocapsules. The additional delivery system(s) may differ in kind fromthe microcapsules. For example, wherein the microcapsule are friable andencapsulate a fragrance, the additional delivery system may be anadditional fragrance delivery system, such as a moisture-triggeredfragrance delivery system. Non-limiting examples of moisture-triggeredfragrance delivery systems include cyclic oligosaccharide, starch (orother polysaccharide material), or combinations thereof.

Starch

Examples of starches suitable for use can be made from raw starch,pregelatinized starch, modified starch derived from tubers, legumes,cereal and grains for example corn starch, wheat starch, rice starch,waxy corn starch, oat starch, cassava starch, waxy barley starch, waxyrice starch, sweet rice starch, amioca, potato starch, tapioca starch,and mixtures thereof. Further examples of modified starches may includehydrolyzed starch, acid thinned starch, starch having hydrophobicgroups, such as starch esters of long chain hydrocarbons (C5 orgreater), starch acetates, starch octenyl succinate, and mixturesthereof. An example of starch esters includes starch octenyl succinates.

Starch esters will typically have a degree of substitution in the rangeof from 0.01% to 10%. The hydrocarbon part of the modifying ester can bea C 5 to a C 16 carbon chain. As stated above, one example of a starchester is octenyl succinate. The octenyl succinate (OSAN) can be asubstituted waxy corn starch of various types such as 1) waxy starch,acid thinned and OSAN substituted, 2) blend of corn syrup solids: waxystarch, OSAN substituted and dextrinized, 3) waxy starch: OSANsubstituted and dextrinised, 4) blend of corn syrup solids ormaltodextrins with waxy starch: acid thinned OSAN substituted thencooked and spray dried, 5) waxy starch: acid thinned OSAN substitutedthen cooked and spray dried; and 6) the high and low viscosities of theabove modifications (based on the level of acid treatment) can also beused. Mixtures of these, particularly mixtures of the high and lowviscosity modified starches, are also suitable.

The term “hydrolyzed starch” refers to oligosaccharide-type materialsthat are typically obtained by acid and/or enzymatic hydrolysis ofstarches, like corn starch. A starch ester may be included in the starchwater-mixture. The hydrolyzed starches, particularly for starch estersor mixture of starch esters, can have Dextrose Equivalent (DE) values offrom 20 to 80, from 20 to 50, or even 25 to 38 DE. The DE value is ameasure of the reducing equivalence of the hydrolyzed starch referencedto dextrose and expressed as a percent (on a dry basis). The higher theDE value, the more reducing sugars present. A method for determining DEvalues can be found in Standard Analytical Methods of the MemberCompanies of Corn Industries Research Foundation, 6th ed. CornRefineries Association, Inc. Washington, D.C. 1980, D-52.

One example of a modified starch comprises a starch derivativecontaining a hydrophobic group, or both a hydrophobic and a hydrophilicgroup, which has been degraded by at least one enzyme capable ofcleaving the 1,4 linkages of the starch molecule from the non-reducingends to produce short chained saccharides to provide high oxidationresistance while maintaining substantially high molecular weightportions of the starch base. Such starches are described in EP-A-922449.

Starches may also comprise monosaccharides such as glucose,disaccharides, trisaccharides, oligosaccharides, polysaccharides, andlinear sugar alcohols such as mannite. As for the polysaccharides,mention may be made of starch, cellulose, chitin, chitosan,hemicellulose, pectin, pullulan, agar, alginic acid, carageenan,dextrin, trehalose, and the like.

Cyclic Oligosaccharide

As used herein, the term “cyclic oligosaccharide” means a cyclicstructure comprising six or more saccharide units. The cyclicoligosaccharides may have six, seven, or eight saccharide units ormixtures thereof. It is common in the art to refer to six, seven andeight membered cyclic oligosaccharides as α, β, and γ, respectively. Thecyclic oligosaccharides that may be useful include those that aresoluble in water, ethanol, or both water and ethanol. The cyclicoligosaccharides useful herein may have a solubility of at least about0.1 g/100 ml, at 25° C. and 1 atm of pressure in either water, ethanol,or both water and ethanol. The personal care compositions disclosedherein may comprise from about 0.001% to about 40%, from about 0.1% toabout 25%, from about 0.3% to about 20%, from about 0.5% to about 10%,or from about 0.75% to about 5%, by weight of the personal carecomposition, of a cyclic oligosaccharide. The personal care compositionsdisclosed herein may comprise from 0.001% to 40%, from 0.1% to 25%, from0.3% to 20%, from 0.5% to 10%, or from 0.75% to 5%, by weight of thepersonal care composition, of a cyclic oligosaccharide.

The cyclic oligosaccharide may comprise any suitable saccharide ormixture of saccharides. Examples of suitable saccharides include, butare not limited to, glucose, fructose, mannose, galactose, maltose, andmixtures thereof. The cyclic oligosaccharide, or mixture of cyclicoligosaccharides, may be substituted by any suitable substituent ormixture of substituents. Herein, the use of the term “mixture ofsubstituents” means that two or more different suitable substituents maybe substituted onto one cyclic oligosaccharide. Suitable examples ofsubstituents include, but are not limited to, alkyl groups, hydroxyalkylgroups, dihydroxyalkyl groups, carboxyalkyl groups, aryl groups,maltosyl groups, allyl groups, benzyl groups, alkanoyl groups, andmixtures thereof. These substituents may be saturated or unsaturated,straight or branched chain. For example, the substituents may includesaturated and straight chain alkyl groups, hydroxyalkyl groups, andmixtures thereof. The alkyl and hydroxyalkyl substituents, for example,may also be selected from C₁-C₈ alkyl or hydroxyalkyl groups, alkyl andhydroxyalkyl substituents from C₁-C₆ alkyl or hydroxyalkyl groups, andalkyl and hydroxyalkyl substituents from C₁-C₄ alkyl or hydroxyalkylgroups. The alkyl and hydroxyalkyl substituents may be, for example,propyl, ethyl, methyl, and hydroxypropyl.

In addition to the substituents themselves, the cyclic oligosaccharidesmay have an average degree of substitution of at least 1.6, wherein theterm “degree of substitution” means the average number of substituentsper saccharide unit. For example, the cyclic oligosaccharides may havean average degree of substitution of less than about 2.8 or from aboutto about 2.0. The average number of substituents may be determined usingcommon Nuclear Magnetic Resonance techniques known in the art. Examplesof cyclic oligosaccharides useful herein include cyclodextrins such asmethyl-α-cyclodextrins, methyl-β-cyclodextrins,hydroxypropyl-α-cyclodextrins, hydroxypropyl-β-cyclodextrins, andmixtures thereof. The cyclodextrins may be in the form of particles. Thecyclodextrins may also be spray-dried and may also be spray-driedparticles. The cyclodextrins may also be complexed with a fragrance toform a complexed cyclodextrin.

Fragrances

The personal care compositions may include one or more fragrances. Asused herein, “fragrance” is used to indicate any odoriferous material.Any fragrance that is cosmetically acceptable may be used in thepersonal care composition. For example, the fragrance may be one that isa liquid at room temperature. Generally, the fragrance(s) may be presentat a level from about 0.01% to about 40%, from about 0.1% to about 25%,from about 0.25% to about 20%, or from about 0.5% to about 15%, byweight of the personal care composition.

A wide variety of chemicals are known as fragrances, includingaldehydes, ketones, and esters. More commonly, naturally occurring plantand animal oils and exudates comprising complex mixtures of variouschemical components are known for use as fragrances. Non-limitingexamples of the fragrances useful herein include pro-fragrances such asacetal pro-fragrances, ketal pro-fragrances, ester pro-fragrances,hydrolyzable inorganic-organic pro-fragrances, and mixtures thereof. Thefragrances may be released from the pro-fragrances in a number of ways.For example, the fragrance may be released as a result of simplehydrolysis, or by a shift in an equilibrium reaction, or by a pH-change,or by enzymatic release. The fragrances herein may be relatively simplein their chemical make-up, comprising a single chemical, or may comprisehighly sophisticated complex mixtures of natural and synthetic chemicalcomponents, all chosen to provide any desired odor.

The fragrances may have a boiling point (BP) of about 500° C. or lower,about 400° C. or lower, or about 350° C. or lower. The BP of manyfragrances are disclosed in Perfume and Flavor Chemicals (AromaChemicals), Steffen Arctander (1969). The C log P value of thefragrances may be about 0.1 or greater, about 0.5 or greater, about 1.0or greater, and about 1.2 or greater. As used herein, “C log P” meansthe logarithm to the base 10 of the octanol/water partition coefficient.The C log P may be readily calculated from a program called “C LOG P”which is available from Daylight Chemical Information Systems Inc.,Irvine Calif., USA. Octanol/water partition coefficients are describedin more detail in U.S. Pat. No. 5,578,563.

Suitable fragrances are also disclosed in U.S. Pat. Nos. 4,145,184,4,209,417, 4,515,705, and 4,152,272. Non-limiting examples of fragrancesinclude animal fragrances such as musk oil, civet, castoreum, ambergris,plant fragrances such as nutmeg extract, cardomon extract, gingerextract, cinnamon extract, patchouli oil, geranium oil, orange oil,mandarin oil, orange flower extract, cedarwood, vetyver, lavandin, ylangextract, tuberose extract, sandalwood oil, bergamot oil, rosemary oil,spearmint oil, peppermint oil, lemon oil, lavender oil, citronella oil,chamomille oil, clove oil, sage oil, neroli oil, labdanum oil,eucalyptus oil, verbena oil, mimosa extract, narcissus extract, carrotseed extract, jasmine extract, olibanum extract, rose extract, andmixtures thereof.

Other examples of suitable fragrances include, but are not limited to,chemical substances such as acetophenone, adoxal, aldehyde C-12,aldehyde C-14, aldehyde C-18, allyl caprylate, ambroxan, amyl acetate,dimethylindane derivatives, α-amylcinnamic aldehyde, anethole,anisaldehyde, benzaldehyde, benzyl acetate, benzyl alcohol and esterderivatives, benzyl propionate, benzyl salicylate, borneol, butylacetate, camphor, carbitol, cinnamaldehyde, cinnamyl acetate, cinnamylalcohol, cis-3-hexanol and ester derivatives, cis-3-hexenyl methylcarbonate, citral, citronnellol and ester derivatives, cumin aldehyde,cyclamen aldehyde, cyclo galbanate, damascones, decalactone, decanol,estragole, dihydromyrcenol, dimethyl benzyl carbinol,6,8-dimethyl-2-nonanol, dimethyl benzyl carbinyl butyrate, ethylacetate, ethyl isobutyrate, ethyl butyrate, ethyl propionate, ethylcaprylate, ethyl cinnamate, ethyl hexanoate, ethyl valerate, ethylvanillin, eugenol, exaltolide, fenchone, fruity esters such as ethyl2-methyl butyrate, galaxolide, geraniol and ester derivatives, helional,2-heptonone, hexenol, α-hexylcinnamic aldehyde, hydroxycitrolnellal,indole, isoamyl acetate, isoeugenol acetate, ionones, isoeugenol,isoamyl iso-valerate, iso E super, limonene, linalool, lilial, linalylacetate, lyral, majantol, mayol, melonal, menthol, p-methylacetophenone,methyl anthranilate, methyl cedrylone, methyl dihydrojasmonate, methyleugenol, methyl ionone, methyl-α-naphthyl ketone, methylphenylcarbinylacetate, mugetanol, γ-nonalactone, octanal, phenyl ethyl acetate,phenyl-acetaldehyde dimethyl acetate, phenoxyethyl isobutyrate, phenylethyl alcohol, pinenes, sandalore, santalol, stemone, thymol, terpenes,triplal, triethyl citrate, 3,3,5-trimethylcyclohexanol, γ-undecalactone,undecenal, vanillin, veloutone, verdox, and mixtures thereof.

Other Materials

The personal care compositions may also include other materials knownfor use in antiperspirant, deodorant or other personal care products,including those materials that are known to be suitable for topicalapplication to skin. Non-limiting examples include dyes or colorants,emulsifiers, distributing agents, pharmaceuticals or other topicalactives, skin conditioning agents or actives, deodorant agents,antimicrobials, preservatives, surfactants, processing aides such asviscosity modifiers and wash-off aids.

III. Methods of Use

The personal care compositions including an antiperspirant active may beapplied topically to the underarm or other suitable area of the skin inan amount effective to reduce or inhibit perspiration wetness. Thepersonal care compositions may be applied, for example, in an amountranging from at least about 0.1 gram to about 20 grams, to about 10grams, or to about 1 gram. The personal care composition may also beapplied to the underarm at least about one or two times daily,preferably once daily, to achieve effective antiperspirant reduction orinhibition over an extended period or in an amount such that thefragrance applied is noticeable by the user.

The personal care composition may also be applied every other day, orevery third or fourth day, and then optionally to supplement applicationon off-days with other personal care compositions such as deodorantsand/or conventional antiperspirant formulations.

Personal care compositions may be applied to skin, wherein the volatileanhydrous carrier leaves behind a skin-adhering polymer andactive-containing film. This film is positioned over the sweat ducts andresists flaking and/or rub-off, thereby being present through multipleperspiration episodes.

IV. Methods of Manufacturing

The personal care composition may be prepared by any known or otherwiseeffective technique, suitable for providing the personal carecomposition of the desired form while incorporating the teachingsherein. Many such techniques are described in theantiperspirant/deodorant formulation arts for the described productforms. A few non-limiting examples are provided herein.

Personal care compositions may be made by a batch process. This processgenerally involves adding all of the raw materials (except active andperfume) to a mix tank, heating the materials to a temperature to meltthe structurants and other higher melt point ingredients, and holding itat that temperature until the appropriate ingredients are melted. Thisheating step may involve temperatures of, for example, 80° C. or more,and it may take from 45 minutes to an hour for the ingredients to melt.At this point, the batch is cooled to 70-75° C. and the active andfragrances may be added to the tank. The personal care composition isusually mixed at the temperature of 70-75° C. for at least 15 minutes(and sometimes held at 70-75° C. for 24-72 hours) before being cooled to50-55° C. and poured into, for example, canisters. Typically, thepersonal care composition is kept at or above the temperature thatallows the personal care composition to be in a mobile state as to allowfor transfer of the personal care composition from the main mix tank toindividual canisters. In some cases, the personal care compositionduring the batch process remains in a molten state for a long period oftime and may be kept at temperatures that impact the performance of themicrocapsules.

A batch process to produce personal care compositions containing PMCsmay require monitoring the temperature of the holding tank containingthe personal care composition to ensure the personal care composition isnot subjected to temperatures that are shown herein to impact theperformance of the microcapsules. In this regard, the temperatures ofthe personal care composition containing the microcapsules should not besubjected to temperatures greater than 60° C. for more than 72 hourswhen the microcapsules are polyacrylate microcapsule, and not subject totemperatures greater than 55° C. for more than 72 hours when themicrocapsules' shell include gelatin. In some instances, it may not bedesirable to subject the personal care composition containingmicrocapsules to temperatures exceeding 55° C. for more than 24 hours.In some examples, the personal care composition including PMCs may besubjected to temperatures ranging from 40° C. to 80° C. for one hour orless. In some examples, the personal care composition including PMCs maybe subjected to temperatures ranging from 40° C. to 60° C. for less than72 hours.

Another method of manufacturing the personal compositions describedherein includes a split stream method. This method is described in moredetail below. Referring to FIG. 1, a non-limiting example of a suitablemanufacturing method is shown. The method 100 combines at least twoprocess streams, a first process stream 102 having a first temperatureand second process stream 104 having a second temperature lower than thefirst temperature, within a mixing chamber 106. Due to the differencesin temperature, the first process stream 102 may also be referred to asthe hot stream, while the second process stream 104 may be referred toas the cold stream. As shown in FIG. 1, the first process stream 102ingredients are mixed in a batch tank 108 while the second processstream 104 ingredients are mixed in separate batch tank 110.Conventional equipment, such as, for example, pumps 112 can be used tofacilitate movement of the first and second process streams 102, 104towards and into a mixing chamber 106.

The first process stream 102 may contain, for example, one or morestructurants (e.g., a wax) melted in a solvent, and a surfactant whichare held above the full melting point of the one or more waxes. Thesolvent of the first process stream 102 may be any material that isliquid at the holding temperature of the hot process stream 102 and thatcan essentially completely dissolve the wax structurant. The solvent maybe selected from any of the previously described liquid carriers. Insome instances, the solvent comprises a silicone fluid, such ascyclomethicone and/or dimethicone (also referred to aspolydimethylsiloxane).

The first process stream 102 is preferably heated to a temperaturesufficient to melt the one or more waxes in the solvent. In someexamples, the temperature of the first process stream 102 is from about65° C., 70° C., 75° C. or 80° C. to about 130° C., 120° C., 110° C.,100° C. or 90° C. within the tank 108 or a static mixer used to combinethe ingredients of the first process stream 102. In some instances wherethe waxes are selected from the group consisting of stearyl alcohol,hydrogenated castor oil, ozokerite, synthetic wax, tribehenin, or C18-36triglyceride and mixtures thereof, the temperature of the first processstream within the tank 108 (or static mixer), is from about 75° C. toabout 95° C. or from about 80° C. to about 95° C.

A second process stream 104 may contain the balance of the liquidcarriers, an antiperspirant active and any heat-sensitive components.The step of forming a second process stream can involve mixing anantiperspirant active, as described herein, and a solvent and optionallya heat sensitive component in the second batch tank 110 or a staticmixer. The second stream 104 has a second temperature T_(c) that islower than the temperature T_(h). Preferably, the second batch tank andthe temperature T_(c) are at ambient, although it may be provided atother temperatures such as at least about 20°, 50° or 70° C. lower thanthe temperature T_(h). In instances where the waxes incorporated intothe first process stream are selected from the group consisting ofstearyl alcohol, hydrogenated castor oil, ozokerite, and mixturesthereof, the temperature of the second process stream within the tank110 (or static mixer), is from about 20° C. to about 40° C. or fromabout 20° C. to about 30° C.

The second process stream 104 may include a liquid emollient or solvent,which may be selected from the various liquid carriers described above.A few non-limiting examples include mineral oil; PPG-14 butyl ether;isopropyl myristate; petrolatum; butyl stearate; cetyl octanoate; butylmyristate; myristyl myristate; C12-15 alkylbenzoate (e.g., Finsolv™);octyldodecanol; isostearyl isostearate; octododecyl benzoate; isostearyllactate; isostearyl palmitate; isobutyl stearate; dimethicone, and anymixtures thereof.

The second process stream 104 may also optionally comprise any heatsensitive component that could chemically degrade or deteriorate orreact with components of the antiperspirant composition at elevatedtemperatures or corrode metal process equipment at elevated storagetemperatures.

The second process stream 104 may also include fragrance-loadedmicrocapsules. In some examples, the temperature of the second processstream within the tank 110 (or static mixer), is less than less than 75°C., less than 70° C., less than 60° C., less than 50° C. but greaterthan 0° C. In some examples, the second process stream 104 including thefragrance-loaded microcapsules may be at about 20° C. to about 40° C. Insome examples, the second process stream 104 including thefragrance-loaded microcapsules does not exceed 80° C. In some examples,the microcapsules may be combined with at least one of an anhydrousliquid carrier and gelling agent prior to incorporation into the secondprocess stream 104. In some examples, the microcapsules may be in theform of a powder with a water content of less than 15% by weight of thepowder when the microcapsules are added to the second process stream104. To produce said powder, the microcapsules may be dried from aslurry including greater than 15% water by centrifugation, batch orpressure filtration, tray drying, oven drying, spray drying, or anyother form of drying.

The first process stream 102 and the second process stream 104 arecombined in, or just prior to entering, the mixing chamber 106. Themixing chamber 106 may comprise a pipe, or any other suitablearrangement capable of receiving both the first process stream 102 andthe second process stream 104 therein so that the streams are combinedtherein with sufficient turbulence to cause thorough mixing and heattransfer. By controlling the ratio of the first process stream 102 tothe second process stream 104 at the mixing chamber 106, it is possibleto control the temperature T_(e) of the mixture exiting the mixingchamber 106. The mixing chamber 106 may be a small void space containingstatic baffles 114 or other physical structure arranged to enablesubstantial and/or thorough mixing and heat transfer between the firstand second streams 102, 104. The first and second process streams 102,104 may be introduced into the mixing chamber 106 in an opposed manner,one example of which is shown in FIG. 1, where the streams enter themixing chamber at about 180° C. apart so that impaction of streams maysignificantly enhance their rapid mixing. While the first and secondprocess streams 102, 104 are shown entering the mixing chamber in anopposed manner, it will be appreciated that other arrangements may beutilized.

Upon exiting the mixing chamber 106, the mixture flows to an injector120, which may take the form of piston pump, which pushes a volume ofthe hot mixture into a dispensing package. The injector 120 has a nozzle122 having an exit opening through which the mixture is ejected oressentially poured or cast into the dispensing package at atmosphericpressure. Since the mixture upon exiting the nozzle 122 is still hot andhas a look and consistency similar to milk, the pressure used todispense the mixture from the nozzle can be very low (e.g. 10 psig, 5psig, 4 psig or even 2 psig or less), although it is contemplated thatother pressures within the injector 120 might be utilized if desired. Insome instances, the mixture is able to self level within the dispensingpackage prior to solidifying. In some instances, only a single mixtureor casting step is utilized to fill the dispensing package in order toform a single phase solid stick antiperspirant composition.

Dispensing packages 125 may be maneuvered into position for filling byany means known in the art, including a conveyor 130. The dispensingpackages 125 may be filled by top or bottom filling, as known in theart. A description of some examples of top and bottom filling processesis provided in commonly assigned USPN 2013/170886. The antiperspirantcompositions cool within the dispensing package to ambient temperatureto thereby form a solid stick antiperspirant composition.

The step of combining the at least one first process stream and the atleast one second process stream together involves combining the streamsin such a manner which may cause substantially complete mixing and heattransfer between the first process stream and the second process streamin a very short time period. The time period during which such mixingand heat transfer occur may be less than 3 seconds, more specificallyless than 1 second, although longer mix times may also be used.

As discussed above, the temperature T_(e) of the mixture exiting themixing chamber 106 is preferably still hot. In some instances, themixture exiting the mixing chamber may be from 10° C. to 15° C. or moreabove the onset of crystallization of the solid stick antiperspirantcomposition. In some instances, the mixture upon exiting the nozzle 122may have an exit temperature from about 55° C. to about 60° C. or more.The mixture cools within the dispensing package, at which point one ormore of the structurants may begin to crystallize. Preferably, completemixing of the first process stream and the second process stream occurswithin 3.5 inches, 2 inches or 1 inch of the where the first processstream and the second process stream enter the mixing chamber 106.

The temperature of the first process stream, the second process stream,and the resulting combined, product stream can be measured by any methodknown in the art. The temperature of the first process stream T_(h) andthe temperature of the second process stream T_(c) can be measured justbefore the two streams enter the mixing chamber 106 or otherwisecombine; and the temperature T_(e) of the mixture can be measured rightafter the first and second process streams have been combined and exitthe mixing chamber.

While the split stream method is described herein with regard to twoprocess streams, it will be appreciated that the process is not limitedto mixing just two process streams; one skilled in the art willunderstand that each of the first and second process streams maycomprise several first and second process streams. Put another way, thepresent invention contemplates mixing multiple first process streams andmultiple second process streams.

Late Point Product Differentiation

Late point product differentiation may also be utilized for maintainingthe efficacy of the PMCs in the personal care composition. Late pointproduct differentiation involves deferring when the end-product acquiresits unique identities. With regards to the addition of microcapsules,this may involve the addition of the microcapsules into the finishedproduct stream as the finished product stream is transferred from alarger, making system tank, into a smaller surge/holding tank, prior todispensing into one or more canisters. The product temperature, uponincorporation of the microcapsules, may be decreased to a temperaturebelow 75° C. or that temperature that promotes the degradation of theperformance of the microcapsules. Non-limiting examples include addingthe microcapsules to the personal care composition when the temperatureof the personal care composition is less than 80° C., less than 70° C.,less than 60° C., less than 55° C., or less than 50° C., but above thetemperature at which point the personal care composition solidifies,usually in the range of 20−50° C. The microcapsules may be incorporatedvia a high speed disperser, which generates a vacuum to draw themicrocapsules into the fluid flow-path. Complete homogenization of themicrocapsule-containing finished product may then occur in the disperserprior to entering the surge/holding tank. Product temperature may bemaintained in the surge tank below that which promotes the degradationof the microcapsules. The product may then be dispensed into individualcanisters and control-cooled to generate the product's characteristicsand attributes, thus minimizing the microcapsules exposure to elevatedtemperatures.

V. Headspace Test Method

Sample Preparation

1. For each personal care composition to be tested, prepare at least oneProfessional Aerosol Testing cardboard blotter card of 7.6×12.7 cm size,available from Orlandi Inc. (Farmingdale, N.Y., USA). (Additionally,prepare one ‘control blotter’ for fragrance(s) to be tested andtracked). Between 0.23-0.27 g of finished product composition should beapplied to the blotter cards for sampling.Before applying the personal care composition to the blotter cards,prepare or prime the dispensing device according to package directions.For a cream/conditioning/semi-solid product, expose the product untilthe finished product is seen coming through all dispensing holes in thedevices' application surface, then wipe the application surface cleanwith a paper towel. For an invisible solid product, expose the productuntil the top rounded dome of the stick is fully exposed and then removethe exposed dome from the stick with a cutting wire by sliding acrosstop of packaging, to achieve a flat surface on the stick of product. Forfluids, powders, and aerosols, proceed to next step.2. Pre-weigh each blotter card with an analytical balance. Apply thepersonal care composition evenly to the inner part of the blotter(leaving a 1.3 cm wide zone without product around the outside edge ofthe blotter card). This may involve spraying or pipetting, for example,depending on the state of the product (e.g. gas or liquid). Continueapplying until between 0.23-0.27 g of the personal care composition isapplied, using a balance to determine the weight. For invisible solidproducts, expose the cleanly cut stick surface until approximately 0.3cm of the finished product is exposed above the packaging material, thenapply the personal care composition evenly in a circular motion to theinner part of the blotter card, leaving a 1.3 cm wide zone withoutproduct around the outside edge of the blotter card. Continue applyinguntil 0.23-0.27 g of the personal care composition is applied, using thebalance to determine the weight. If the personal care composition doesnot appear evenly distributed across the application area upon visualevaluation, dispose of the blotter card and repeat the applicationprocess with a new card.3. Repeat steps 1 and 2 for each personal care composition to besampled.4. Once all blotter cards have been prepared for each personal carecomposition to be sampled, lay the cards out on paper towels or othersubstrate with finished product side exposed overnight (18-24 hours)before conducting the zNose evaluation.5. After the drydown period, roll each blotter card into a cylindershape across the long axis of the card and put into a 207 mL clearpolyethylene terephthalate disposable beverage cup with lid, such asavailable from Solo Cup Company (Lake Forest, Ill., USA). Arrange thecard so the finished product side of the blotter is facing the inside ofthe cup. Close the lid. Repeat for all blotter cards. Samples are nowprepped and in a controlled headspace ready for evaluation

zNose Evaluation

1. Prepare the 7100 Benchtop zNose Fast-GC Analyzer (Model # MEA007100with MicroSenseESTCal System Software version 5.44.28) with DB-624column, or equivalent, as available from Electronic Sensor TechnologyInc. (Newbury Park, Calif., USA), for evaluations, as defined inmanufacturer's instructions.2. Turn on zNose and perform daily cleaning steps. zNose is clean andoperational when all ‘peaks’ are below 100 counts per mfr instructions.3. Ensure ‘Test Settings’ are set according to the following:

a. Sensor: 60° C. for fluids (40° C. for all else including FinishedProduct Soft Solid/Invisible Solid)

b. Column: 40° C.

c. Valve: 145° C.

d. Inlet: 200° C.

e. Trap: 200° C.

f. Pump Time: 10 seconds

4. Once the test settings match the above requirements, calibrate thezNose with a n-alkanes standard. This will ensure zNose is operatingaccording to manufacturer standard.5. Once cleaned and calibrated, create a new alarm file. The new alarmfile will contain no tagged peaks. Remove ‘control blotter’ from the cupthen fold the card in half with the finished product application side onthe inside. Using both hands, rub the outside of the folded card withthe force required to break an egg, using a back and forth motion tentimes, to cover the whole of one side of the folded card. Return thecard to its cup, and re-seal. Run ‘control blotter’ from Step 1according to manufacturer instructions. Tag all fragrance peaks below1200 KI (Kovats Index). If no ‘control blotter’ is available forfragrance to be tested, all peaks (including baseline peaks fromcomposition and peaks >1200 KI) must be tracked6. Sampling order should be selected at random from all the samples tobe tested.7. For each cup to be sampled, remove blotter from the cup then fold thecard in half with the finished product application side on the inside.Using both hands, rub the outside of the folded card with the forcerequired to break an egg, using a back and forth motion ten times, tocover the whole of one side of the folded card. Return the card to itsrespective cup, and re-seal. Then immediately analyze said cup on thezNose with one run according to the manufacturer's instructions. Afteranalysis, run a cleaning by bubbling methanol for 10 seconds. Repeatuntil all cups tested.8. Once all cups have been tested, transfer all data to a spreadsheetand sum the total area under all peaks associated with the fragrance (orsum all peaks including baseline peaks if no ‘control blotter’ wastested).9. For each cup tested, the analyses will result in a total fragrancepeak area <1200 KI measurement by summing all tagged fragrance peaks<1200 KI in a new column. (If multiple replicates tested, calculate theaverage of all replicates, standard deviation, and % Relative StandardDeviation (% RSD)). The average of all replicates is the Total fragrancepeak area <1200 KI for each respective personal care composition. If nocontrol blotter was available to tag fragrance peaks, sum all of thepeaks in a new column for tracking.10. Each personal care composition should have a total fragrance peakarea <1200 KI (or total peak area for personal care compositions without‘control blotters’).

VI. Static Yield Stress/High Shear Viscosity

To determine static stress yield values for the personal carecompositions herein, a two-part test may be conducted. First, acontrolled stress ramp may ramp up linearly, and may measure a shearrate at each point of stress. In the second part of the two-part test, acontrolled shear rate ramp may be linearly increased and shear stressmay be measured. A rheological model may be used to fit the data in bothsegments of the test, and a value may be determined from the rheologicalmodel for both segments.

Personal care compositions are collected after they have been dispensedthrough their consumer use package and may be analyzed using arheometer. In particular, the rheometer may be a Thermo Scientific HaakeRheoStress 600 (available from TA Instruments, New Castle, Del., U.S.A)and data collection and analysis may be performed using rheologysoftware, which may be RheoWin Software Version 2.84 or greater.

To prepare product samples, each product sample may be conditioned atabout 23° C. until rheological properties may stabilize. An incubationperiod may be specified for each type of antiperspirant soft solidcomposition.

To operate the rheometer, parallel plates may be installed, and usingthe rheology software, a zero point for a gap between the parallelplates may be determined. A sufficient amount of the product sample maybe loaded to ensure that entire serrated portions of the parallel platesmay be in contact with the product sample once the product sample may bein a measurement position. A spatula may be used to carefully scrapedispensed product onto the serrated portion of a base plate. Once theproduct may be loaded, the rheology software may be used to move theparallel plates. A controlled stress ramp may be conducted followed by acontrolled shear rate ramp.

Next, the rheology software may be used to determine shear yield stressvalues based on the controlled stress ramp and the controlled shear rateramp. Data from the rheology test may be plotted as viscosity (Pa-s) ona log scale versus linear applied stress (Pa). “Static yield stress”refers to a point in a stress sweep analysis of a product at which pointthe rheometer is first capable of measuring product viscosity. Thestatic yield stress is extrapolated from the data from a flow regionalong a shear rate measurement within 50-5001/s.

VII. Fracture Strength Test Method

One skilled in the art will recognize that various protocols may beconstructed for the extraction and isolation of microcapsules fromfinished products, and will recognize that such methods requirevalidation via a comparison of the resulting measured values, asmeasured before and after the microcapsules' addition to and extractionfrom the finished product. The isolated microcapsules are thenformulated in de-ionized (DI) water to form a slurry forcharacterization.

To calculate the percentage of microcapsules which fall within a claimedrange of fracture strengths, three different measurements are made andtwo resulting graphs are utilized. The three separate measurements arenamely: i) the volume-weighted particle size distribution (PSD) of themicrocapsules; ii) the diameter of at least 10 individual microcapsuleswithin each of 3 specified size ranges, and; iii) the rupture-force ofthose same 30 or more individual microcapsules. The two graphs createdare namely: a plot of the volume-weighted particle size distributiondata collected at i) above; and a plot of the modeled distribution ofthe relationship between microcapsule diameter and fracture-strength,derived from the data collected at ii) and iii) above. The modeledrelationship plot enables the microcapsules within a claimed strengthrange to be identified as a specific region under the volume-weightedPSD curve, and then calculated as a percentage of the total area underthe curve.

-   -   a.) The volume-weighted particle size distribution (PSD) of the        microcapsules is determined via single-particle optical sensing        (SPOS), also called optical particle counting (OPC), using the        AccuSizer 780 AD instrument, or equivalent, and the accompanying        software CW788 version 1.82 (Particle Sizing Systems, Santa        Barbara, Calif., U.S.A.). The instrument is configured with the        following conditions and selections: Flow Rate=1 ml/sec; Lower        Size Threshold=0.50 μm; Sensor Model Number=LE400-05SE;        Autodilution=On; Collection time=120 sec; Number channels=512;        Vessel fluid volume=50 ml; Max coincidence=9200. The measurement        is initiated by putting the sensor into a cold state by flushing        with water until background counts are less than 100. A capsule        slurry, and its density of particles is adjusted with DI water        as necessary via autodilution to result in particle counts of at        least 9200 per ml. During a time period of 120 seconds the        suspension is analyzed. The resulting volume-weighted PSD data        are plotted and recorded, and the values of the mean, 5^(th)        percentile, and 90^(th) percentile are determined.    -   b.) The diameter and the rupture-force value (also known as the        bursting-force value) of individual microcapsules are measured        via a computer-controlled micromanipulation instrument system        which possesses lenses and cameras able to image the        microcapsules, and which possesses a fine, flat-ended probe        connected to a force-transducer (such as the Model 403A        available from Aurora Scientific Inc, Canada, or equivalent), as        described in: Zhang, Z. et al. (1999) “Mechanical strength of        single microcapsules determined by a novel micromanipulation        technique.” J. Microencapsulation, vol 16, no. 1, pages 117-124,        and in: Sun, G. and Zhang, Z. (2001) “Mechanical Properties of        Melamine-Formaldehyde microcapsules.” J. Microencapsulation, vol        18, no. 5, pages 593-602, and as available at the University of        Birmingham, Edgbaston, Birmingham, UK.    -   c.) A drop of the microcapsule suspension is placed onto a glass        microscope slide, and dried under ambient conditions for several        minutes to remove the water and achieve a sparse, single layer        of solitary particles on the dry slide. Adjust the concentration        of microcapsules in the suspension as needed to achieve a        suitable particle density on the slide. More than one slide        preparation may be needed.    -   d.) The slide is then placed on a sample-holding stage of the        micromanipulation instrument. Thirty or more microcapsules on        the slide(s) are selected for measurement, such that there are        at least ten microcapsules selected within each of three        pre-determined size bands. Each size band refers to the diameter        of the microcapsules as derived from the Accusizer-generated        volume-weighted PSD. The three size bands of particles are: the        Mean Diameter+/−2 μm; the 5^(th) Percentile Diameter+/−2 μm; and        the 90^(th) Percentile Diameter+/−2 μm. Microcapsules which        appear deflated, leaking or damaged are excluded from the        selection process and are not measured.    -   e.) For each of the 30 or more selected microcapsules, the        diameter of the microcapsule is measured from the image on the        micromanipulator and recorded. That same microcapsule is then        compressed between two flat surfaces, namely the flat-ended        force probe and the glass microscope slide, at a speed of 2 μm        per second, until the microcapsule is ruptured. During the        compression step, the probe force is continuously measured and        recorded by the data acquisition system of the micromanipulation        instrument.    -   f.) The cross-sectional area is calculated for each of the        microcapsules, using the diameter measured and assuming a        spherical particle (πr², where r is the radius of the particle        before compression). The rupture force is determined for each        sample by reviewing the recorded force probe measurements. The        measurement probe measures the force as a function of distance        compressed. At one compression, the microcapsule ruptures and        the measured force will abruptly stop. This maxima in the        measured force is the rupture force.    -   g.) The Fracture Strength of each of the 30 or more        microcapsules is calculated by dividing the rupture force (in        Newtons) by the calculated cross-sectional area of the        respective microcapsule.    -   h.) On a plot of microcapsule diameter versus fracture-strength,        a Power Regression trend-line is fit against all 30 or more raw        data points, to create a modeled distribution of the        relationship between microcapsule diameter and        fracture-strength.    -   i.) The percentage of microcapsules which have a fracture        strength value within a specific strength range is determined by        viewing the modeled relationship plot to locate where the curve        intersects the relevant fracture-strength limits, then reading        off the microcapsule size limits corresponding with those        strength limits. These microcapsule size limits are then located        on the volume-weighted PSD plot and thus identify an area under        the PSD curve which corresponds to the portion of microcapsules        falling within the specified strength range. The identified area        under the PSD curve is then calculated as a percentage of the        total area under the PSD curve. This percentage indicates the        percentage of microcapsules falling with the specified range of        fracture strengths.

VIII. Examples

The following examples are given solely for the purpose of illustrationand are not to be construed as limiting the invention, as manyvariations thereof are possible.

In the examples, all concentrations are listed as weight percent, unlessotherwise specified and may exclude minor materials such as diluents,filler, and so forth. The listed formulations, therefore, comprise thelisted components and any minor materials associated with suchcomponents. As is apparent to one of ordinary skill in the art, theselection of these minor materials will vary depending on the physicaland chemical characteristics of the particular ingredients selected tomake the present invention as described herein.

Example 1. Nonionic Microcapsules

An oil solution, consisting of 75 g Fragrance Oil scent A, 75 g ofIsopropyl Myristate, 0.6 g DuPont Vazo-52, and 0.4 g DuPont Vazo-67, isadded to a 35° C. temperature controlled steel jacketed reactor, withmixing at 1000 rpm (4 tip, 2″ diameter, flat mill blade) and a nitrogenblanket applied at 100 cc/min. The oil solution is heated to 75° C. in45 minutes, held at 75° C. for 45 minutes, and cooled to 60° C. in 75minutes.

A second oil solution, consisting of 37.5 g Fragrance Oil, 0.25 gtertiarybutylaminoethyl methacrylate, 0.2 g 2-carboxyethyl acrylate, and10 g Sartomer CN975 (hexafunctional urethane-acrylate oligomer) is addedwhen the first oil solution reached 60° C. The combined oils are held at60° C. for an additional 10 minutes.

Mixing is stopped and a water solution, consisting of 56 g of 5% activepolyvinyl alcohol Celvol 540 solution in water, 244 g water, 1.1 g 20%NaOH, and 1.2 g DuPont Vazo-68WSP, is added to the bottom of the oilsolution, using a funnel.

Mixing is again started, at 2500 rpm, for 60 minutes to emulsify the oilphase into the water solution. After milling is completed, mixing iscontinued with a 3″ propeller at 350 rpm. The batch is held at 60° C.for 45 minutes, the temperature is increased to 75° C. in 30 minutes,held at 75° C. for 4 hours, heated to 90° C. in 30 minutes and held at90° C. for 8 hours. The batch is then allowed to cool to roomtemperature. The finished microcapsules have a median particle size of11 microns, a broadness index of 1.3, and a zeta potential of negative0.5 millivolts, and a total scent A concentration of 19.5 wt %, and awater content of 57 wt %.

Example 2. Spray Dried Microcapsules

To 94.85 kilograms of nonionic perfume microcapsule made by the methodof example 1 is added 0.15 kilograms of Xanthan Gum powder (NovaxanDispersible Xanthan Gum Product 174965) at a temperature of 45 degreesCentigrade, while mixing. After 25 minutes of mixing, 4.5 kilograms of a32 wt % solution of magnesium chloride is added to the slurry (over aperiod of 10 minutes), then the slurry is mixed for an additional 30minutes. Next, 1 kilogram of citric acid (anhydrous powder) is added,and mixed for 30 minutes to assure complete dissolution in thecontinuous phase of the slurry. This mixture is then atomized using aco-current Niro dryer, 7 ft diameter, using a rotary centrifugal wheelatomizer. The slurry is dried at an inlet air temperature of 200-220degrees Centigrade, and outlet air temperature of 105-110 degreesCentigrade to yield a powder containing approximately 5 wt % water, abulk density of 380 grams per Liter.

Example 3. 80 wt % Core/20 wt % Wall Urea Based Polyurea Capsule

2 grams of Urea (Sigma Aldrich of Milwaukee, Wis.) is dissolved in 20 gdeionized water. 1 gram of resorcinol (Sigma Aldrich of Milwaukee, Wis.)is added to the homogeneous urea solution. 20 g of 37 wt % formaldehydesolution (Sigma Aldrich of Milwaukee, Wis.) is added to the solution,and the pH of the slurry is adjusted to 8.0 using 1M sodium hydroxidesolution (Sigma Aldrich of Milwaukee, Wis.). The reactants are allowedto sit at 35° C. for 2 hours. In a separate beaker, 80 grams offragrance oil is added slowly to the urea-formaldehyde solution. Themixture is agitated using a Janke & Kunkel Laboretechnik mixer using apitched, 3-blade agitator to achieve a 12 micron mean oil droplet sizedistribution, with a standard deviation of 2 microns. The pH of theslurry is adjusted to 3.0 using 1M Hydrochloric Acid to initiate thecondensation reaction. The solution is heated to 65° C. and allowed toreact in a constant temperature water bath, while slowly agitating thecontents of the mixture. The contents are allowed to react for 4 hoursat 65° C.

Example 4. 90% Core/10 wt % Wall Melamine Based Polyurea Capsule

A first mixture is prepared by combining 208 grams of water and 5 gramsof alkyl acrylate-acrylic acid copolymer (Polysciences, Inc. ofWarrington, Pa., USA). This first mixture is adjusted to pH 5.0 usingacetic acid.

280 grams of the capsule core material which comprise a fragrance oil isadded to the first mixture at a temperature of 45° C. to form anemulsion. The ingredients to form the capsule wall material are preparedas follows: 9 grams of a corresponding capsule wall material copolymerpre-polymer (butylacrylate-acrylic acid copolymer) and 90 grams of waterare combined and adjusted to pH 5.0. To this mixture is added 28 gramsof a partially methylated methylol melamine resin solution (“Cymel 385”,80% solids, Cytec). This mixture is added to the above describedfragrance oil-in-water emulsion with stirring at a temperature of 45degrees Centigrade. High speed blending is used to achieve a volume-meanparticle size of 12 micron, and a standard deviation of 2.6 microns. Thetemperature of the mixture is gradually raised to 65 degrees Centigrade,and is maintained at this temperature overnight with continuous stirringto initiate and complete encapsulation.

To form the acrylic acid-alkyl acrylate copolymer capsule wall, thealkyl group can be selected from ethyl, propyl, butyl, amyl, hexyl,cyclohexyl, 2-ethylhexyl, or other alkyl groups having from one to aboutsixteen carbons, preferably one to eight carbons.

Example 5. Gelatin-Gum Arabic Capsules

A gum solution is prepared by adding 1.84 grams of carboxymethylcellulose sodium salt and 0.205 grams of gum Arabic FCC powder into87.20 g of deionized water at a temperature of 50 degrees Centigrade,while agitating vigorously to prevent the formation of particleaggregates during powder addition. The solution is mixed until ahomogeneous, transparent solution is obtained, then cooled to 35 degreesCentigrade. A gelatin solution is prepared by adding 18.45 grams ofBloom type A gelatin into 163 grams of deionized water at a temperatureof 50 degrees Centigrade. The solution is cooled to 35 degreesCentigrade after the gelatin solids are completely dissolved. The gumsolution is added to the gelatin solution under very low agitation (toprevent frothing/foaming). The pH of the mixture is adjusted to 5.5using 50 wt % sodium hydroxide solution or 50 wt % citric acid solution.Approximately 180 grams of perfume oil is then added to the mixture.High agitation is pursued to achieve an volume average median dropletsize of the perfume oil between 10-20 micrometers (Accusizer utilized).The solution is cooled at a rate of approximately 0.2 degrees Celsiusper minute to a temperature of 28 degrees Centigrade. The pH of thesolution is also slowly adjusted to 4.0 using 50 wt % citric acid. Oncethe polymer is observed to precipitate out of solution, the solutiontemperature is further lowered to 10 degrees Centigrade. Approximately1.51 grams of 50 wt % glutaraldehyde (Sigma Aldrich) is added to themixture, the temperature of the mixture is raided to 20 degreesCentigrade. The mixture is agitated slowly for a period of 16 hours tocrosslink the shell. This aqueous suspension of gelatin microcapsulescan be optionally spray dried to yield a powder.

Examples A Through F

The following examples illustrated in Table 1a are formulation examplescontaining microcapsules. Examples A, B and C are anhydrous,antiperspirant compositions including spray-dried polyacrylatemicrocapsules made by interfacial polymerization, wherein themicrocapsules encapsulate a fragrance and a quantity of non-volatileoils. Examples D and E are anhydrous compositions containing spray-driedpolyacrylate microcapsules made by interfacial polymerization, whereinthe microcapsules encapsulate a fragrance and a quantity of non-volatileoils. Example F is an anhydrous composition including spray-driedmicrocapsules made by a complex coacervation process that comprisesreacting gelatin with an anionic colloid gum Arabic, and crosslinkingwith gluteraldehyde; wherein the spray-dried microcapsules encapsulate afragrance.

Examples A and B were prepared by a batch process by adding all of theraw materials (except aluminum zirconium trichlorohydrex glycine powder,fragrance, and polyacrylate microcapsules) to a mix tank, heating thematerials to a temperature of 80° C. to melt the structurants and otherhigher melting point ingredients, and maintaining that temperature untilthe ingredients are melted. Once melted, the batch is cooled to 70-75°C. and the aluminum zirconium trichlorohydrex glycine powder, fragrance,and polyacrylate microcapsules are added to the tank. The batch is thenmixed for at least 15 minutes before cooling to 50-55° C. and pouringinto canisters.

Example C was prepared by a split stream process. In the hot streamtank, the waxes (stearyl alcohol, castor wax, ozokerite, behenylalcohol), emollients (C12-15 Alkyl benzoate,) and a lesser portion ofthe cylopentasilaxane are added into one tank, mixed, and then heated to88° C. to melt the waxes. In the cold stream tank, the powders (actives,talc, cyclodextrins, spray-dried microcapsules), fragrances, PPG-14butyl ether, and a greater portion of the cyclopentasiloxane are addedand mixed and maintained at a temperature of less than 50° C. Once eachof the hot and cold streams each is relatively homogenous, each of theprocess streams are simultaneously fed into a static mixer where the twostreams are combined for about 5 seconds or less, ensuring a homogenouspersonal care composition while minimizing the mix time above the waxcrystallization temperature. The personal care composition then exitsthe static mixer into individual canisters where the product is allowedto cool to room temperature.

Examples D, E and F are prepared in a batch process by conventionalmixing techniques.

TABLE 1A Example B Example C Example A Polyacrylate PolyacrylatePolyacrylate PMC in PMC in PMC in Soft Invisible Invisible Example DExample E Example F Solid made Solid made Solid made PolyacrylatePolyacrylate Gelatin PMC via batch via batch via Split PMC in PMC in inprocess process Stream cyclopentasiloxane Dimethicone DimethiconeAluminum 26.5 25.6 — — — — Zirconium Trichlorohydrex Glycine PowderAluminum — — 25.6 — — — Zirconium Tetrachlorohydrex GlyCyclopentasiloxane QS QS QS 98 — — Dimethicone 5 — — 98 98 CO-1897Stearyl — 13 13 — — — Alcohol NF Ozokerite Wax SP- — 1.0 1.0 — — — 1026Type Hydrogenated — 2.90 2.90 — — — Castor Oil MP80 Deodorized BehenylAlcohol — 0.2 0.2 — — — Tribehenin 4.5 — — — — — C 18-36 acid 1.125 — —— — — triglyceride C12-15 Alkyl — 8.5 8.5 — — — Benzoate PPG-14 Butyl0.5 6.5 6.5 — — — Ether Phenyl — — — — — — Trimethicone White Petrolatum3 — — — — — Mineral Oil — 1.0 — — — — Fragrance 0.75 0.75 0.75 — — —Talc Imperial 250 — 2.5 2.5 — — — USP Fragrance 3 — 3 — — — ComplexedBeta- cyclodextrin Polyacrylate 2.0 2.0 1.5 2.0 2.0 — MicrocapsuleGelatin — — — — — 2.0 Microcapsule Acetyl — — 0.01 — — — Glucosamined-Panthenyl — — 0.01 — — — Triacetate DL-ALPHA — — 0.01 — — — TocopherylAcetate (Vit E) QS - indicates that this material is used to bring thetotal to 100%.

Examples G Through I

The following examples illustrated in Table 1b are formulation examplescontaining microcapsules and a starch encapsulated accord. Examples G,H, and I are anhydrous, antiperspirant compositions including asurfactant, Performathox 450 ethoxylate, a spray-dried polyacrylatemicrocapsules made by interfacial polymerization, wherein themicrocapsules encapsulate a fragrance and a quantity of non-volatileoils and a starch encapsulates a fragrance as described below.

Examples G and H were prepared by a batch process by adding all of theraw materials (except aluminum zirconium trichlorohydrex glycine powder,fragrance, polyacrylate microcapsules, and starch encapsulated accord)to a mix tank, heating the materials to a temperature of 88° C. to meltthe structurants, performathox 450 ethoxylate and other higher meltingpoint ingredients, and maintaining that temperature until theingredients are melted. Once melted, the batch is cooled to 70-75° C.and the aluminum zirconium trichlorohydrex glycine powder, fragrance,polyacrylate microcapsules and starch encapsulated accord are added tothe tank. The batch is then mixed for at least 15 minutes before coolingto 50-55° C. and pouring into canisters.

Example I was prepared by a split stream process. In the hot streamtank, the waxes (stearyl alcohol, castor wax, ozokerite, behenylalcohol), emollients (C12-15 Alkyl benzoate), performathox 450ethoxylate and a lesser portion of the cylopentasilaxane are added intoone tank, mixed, and then heated to 88° C. to melt the waxes. In thecold stream tank, the powders (actives, talc, cyclodextrins, spray-driedmicrocapsules, starch encapsulated accord), fragrances, PPG-14 butylether, and a greater portion of the cyclopentasiloxane are added andmixed and maintained at a temperature of less than 50° C. Once each ofthe hot and cold streams each is relatively homogenous, each of theprocess streams are simultaneously fed into a static mixer where the twostreams are combined for about 5 seconds or less, ensuring a homogenouspersonal care composition while minimizing the mix time above the waxcrystallization temperature. The personal care composition then exitsthe static mixer into individual canisters where the product is allowedto cool to room temperature.

TABLE 1b Example G Example H Example I Polyacrylate PMC in PolyacrylatePMC in Polyacrylate PMC in Soft Solid made Invisible Solid madeInvisible Solid made via batch process via batch process via SplitStream Aluminum Zirconium 26.5  24.0 — Trichlorohydrex Glycine PowderAluminum Zirconium — — 25.6 Tetrachlorohydrex Gly Cyclopentasiloxane QSQS QS Dimethicone 5   5 5 CO-1897 Stearyl — 12.3 13.25 Alcohol NFOzokerite Wax SP- — 1.0 1.0 1026 Type Hydrogenated Castor — 2.75 2.90Oil MP80 Deodorized Behenyl Alcohol — 0.2 0.2 Tribehenin 4.5 — — C 18-36acid  1.125 — — triglyceride C12-15 Alkyl — 8.5 8.5 BenzoatePerformathox 450 1.0 1.0 2.0 ethoxylate PPG-14 Butyl Ether 0.5 6.5 6.5White Petrolatum 3   3 3 Mineral Oil — 8.0 8.0 Fragrance  0.75 0.75 0.75Talc Imperial 250 USP — 3 2.5 Fragrance Complexed 2.0 3.0 —Beta-cyclodextrin Polyacrylate 2.0 — 2.0 Microcapsule StarchEncapsulated 1.0 0.8 1.5 Accord QS - indicates that this material isused to bring the total to 100%.

A Starch Encapsulated Accord is made by dissolving 1025 parts of Alcocap300 (Akzo of New Jersey, USA) in 2140 parts of water. Next, 107.9 partsof anhydrous citric acid is dissolved in the solution. 1596 parts offragrance oil is then added, and emulsified using a high shear in-tankArde Barinco homogenizer to yield median volume weighted averageparticles less than 1 microns. The slurry is then spray dried using aco-current Niro spray dryer, centrifugal wheel atomizer, operating at aninlet temperature of 200 degrees Centigrade, and outlet temperature of95 degrees Centigrade, and a slight vacuum in the dryer. Powder iscollected from the cyclone. A yield of about 85% is achieved duringspray drying.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a term in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. An anhydrous stick deodorant composition,comprising: a) one or more non-volatile liquid carriers; b) one or morestructurants having a concentration from about 1% to about 25% by weightof the composition, wherein the one or more structurants comprises oneor more waxes; and c) a moisture-triggered fragrance delivery system;wherein the stick deodorant composition is a single phase.
 2. Theanhydrous stick of claim 1, wherein the one or more non-volatile liquidcarriers comprises a non-volatile silicone.
 3. The anhydrous stick ofclaim 1, wherein the one or more non-volatile liquid carriers comprisesa non-volatile organic fluid.
 4. The anhydrous stick of claim 1, whereinthe anhydrous stick composition is a soft-solid deodorant.
 5. Theanhydrous stick of claim 1, wherein the anhydrous stick composition isan invisible solid deodorant.
 6. The anhydrous stick of claim 1, whereinthe moisture-triggered fragrance delivery system comprises a starch. 7.The anhydrous stick of claim 6, wherein the starch comprises a rawstarch, pregelatinized starch, modified starch, or combination thereof.8. The anhydrous stick of claim 7, wherein the modified starch is a cornstarch.
 9. The anhydrous stick of claim 8, wherein the modified cornstarch is an octenyl succinate.
 10. The anhydrous stick of claim 9,wherein the octenyl succinate comprises a substituted waxy corn starch.11. The anhydrous stick of claim 1, wherein the deodorant compositionfurther comprises a volatile silicone carrier.
 12. The anhydrous stickof claim 1, wherein the deodorant composition comprises from about 1% toabout 20% of the non-volatile liquid carriers.
 13. An anhydrous stickdeodorant composition, comprising: a) one or more non-volatile liquidcarriers; b) one or more structurants having a concentration from about1% to about 25% by weight of the composition, wherein the one or morestructurants comprises one or more waxes; and c) a friable microcapsuledelivery system; wherein the stick deodorant composition is a singlephase.
 14. The anhydrous stick of claim 13, wherein the one or morenon-volatile liquid carriers comprises a non-volatile silicone.
 15. Theanhydrous stick of claim 13, wherein the one or more non-volatile liquidcarriers comprises a non-volatile organic fluid.
 16. The anhydrous stickof claim 13, wherein the anhydrous stick composition is a soft-soliddeodorant or an invisible solid deodorant.
 17. The anhydrous stick ofclaim 13, wherein the friable microcapsule delivery system comprises afragrance.
 18. The anhydrous stick of claim 17, wherein the friablemicrocapsule delivery system comprises a starch, wherein the starchcomprises a raw starch, pregelatinized starch, modified starch, orcombination thereof.
 19. The anhydrous stick of claim 18, wherein themodified starch is a corn starch.
 20. The anhydrous stick of claim 19,wherein the corn starch is an octenyl succinate that comprises asubstituted waxy corn starch.